The heat of hydrogenation of (a) cyclohexatriene [5]

Journal of the American Chemical Society

Volumn 122, Issue 32, 2000, Pages 7819-7820

  Beckhaus, Hans Dieter ^a   Faust, Rüdiger ^b   Matzger, Adam J ^b   Mohler, Debra L ^b   Rogers, Donald W ^c   Rüchardt, Christoph ^a   Sawhney, Ajai K ^b   Verevkin, Sergey P ^a   Vollhardt, K Peter C ^b   Wolff, Stefan ^b  

^a UNIVERSITY OF FREIBURG   (Germany)

^b UNIVERSITY OF CALIFORNIA   (United States)

^c LONG ISLAND UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUND; BENZENE DERIVATIVE; CYCLOHEXENE DERIVATIVE;

CHEMICAL REACTION; CHEMICAL STRUCTURE; ENTHALPY; HYDROGENATION; LETTER; MODEL; THERMODYNAMICS;

EID: 0034674973     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja001274p     Document Type: Letter

References (51)

1. (a) Minkin, V. I.; Glukhovtsev, M. N.; Simkin, B. Ya. Aromaticity and Antiaromaticity; Wiley: New York, 1994.
2. (b) Garratt, P. J. Aromaticity; Wiley: New York, 1986.
3. (a) Brush, S. G. Stud. Hist. Philos. Sci. 1999, 30, 21-79.
4. (b) Brush, S. G. Stud. Hist. Philos. Sci. 1999, 30, 263-302.
5. For selected recent references, see: (a) Wiberg, K. B. In Pauling's Legacy: Modern Modelling of the Chemical Bond; Maksić, Z. B., Orville-Thomas, W. J., Eds.; Elsevier: Amsterdam, 1999; pp 519-536. (b) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531-10536. (c) Mo, Y.; Wu, W.; Zhang, Q. J. Phys. Chem. 1994, 98, 10048-10053.
6. For selected recent references, see: (a) Wiberg, K. B. In Pauling's Legacy: Modern Modelling of the Chemical Bond; Maksić, Z. B., Orville- Thomas, W. J., Eds.; Elsevier: Amsterdam, 1999; pp 519-536. (b) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531-10536. (c) Mo, Y.; Wu, W.; Zhang, Q. J. Phys. Chem. 1994, 98, 10048-10053.
7. For selected recent references, see: (a) Wiberg, K. B. In Pauling's Legacy: Modern Modelling of the Chemical Bond; Maksić, Z. B., Orville- Thomas, W. J., Eds.; Elsevier: Amsterdam, 1999; pp 519-536. (b) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531-10536. (c) Mo, Y.; Wu, W.; Zhang, Q. J. Phys. Chem. 1994, 98, 10048-10053.
8. (d) Glendening, E. D.; Faust, R.; Streitwieser, A.; Vollhardt, K. P. C.; Weinhold, F. J. Am. Chem. Soc. 1993, 115, 10952-10957.
9. See, inter alia: (a) Vollhardt, K. P. C.; Schore, N. E. Organic Chemistry. Structure and Function, 3rd ed.; Freeman: New York, 1999; p 643. (b) McMurry, J. Organic Chemistry, 4th ed.; Brooks-Cole: New York, 1996; p 543. (c) Solomons, T. W. G. Organic Chemistry, 6th ed.; Wiley: New York, 1996; p 621.
10. See, inter alia: (a) Vollhardt, K. P. C.; Schore, N. E. Organic Chemistry. Structure and Function, 3rd ed.; Freeman: New York, 1999; p 643. (b) McMurry, J. Organic Chemistry, 4th ed.; Brooks-Cole: New York, 1996; p 543. (c) Solomons, T. W. G. Organic Chemistry, 6th ed.; Wiley: New York, 1996; p 621.
11. See, inter alia: (a) Vollhardt, K. P. C.; Schore, N. E. Organic Chemistry. Structure and Function, 3rd ed.; Freeman: New York, 1999; p 643. (b) McMurry, J. Organic Chemistry, 4th ed.; Brooks-Cole: New York, 1996; p 543. (c) Solomons, T. W. G. Organic Chemistry, 6th ed.; Wiley: New York, 1996; p 621.
12. Kistiakowsky, G. B.; Ruhoff, J. R.; Smith, H. A.; Vaughan, W. E. J. Am. Chem. Soc. 1936, 58, 146-153 (cf. ref 22).
13. Steele, W. V.; Chirico, R. D.; Knipmeyer, S. E.; Nguyen, A.; Smith, N. K.; Tasker, I. R. J. Chem. Eng. Data 1996, 41, 1269-1284.
14. (a) Diercks, R.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1986, 108, 3150-3152.
15. (b) Holmes, D.; Kumaraswamy, S.; Matzger, A. J.; Vollhardt, K. P. C. Chem. Eur. J. 1999, 5, 3399-3412.
16. (c) For a review of the phenylenes, see: Mohler, D. L.; Vollhardt, K. P. C. In Advances in Strain in Organic Chemistry; Halton, B., Ed.; JAI: London, 1996; Vol. 5, pp 121-160.
17. 7a (a) Bird, C. W. Tetrahedron 1998, 54, 4641-4646.
18. (b) Kovaček, D.; Margetić, D.; Maksić, Z. B. J. Mol. Struct. (THEOCHEM) 1993, 285, 195-210.
19. (c) Baldridge, K. K.; Siegel, J. S. J. Am. Chem. Soc. 1992, 114, 9583-9587.
20. Simply applying [Σ single bond lengths - Σ double bond lengths]/3 as a measure of bond alternation and using the experimental structural data for the exocyclic diene portion of 3,4-dimethylenecydobutene 6 (1.497, 1.338 Å; Brown, R. D.; Godfrey, P. D.; Hart, B. T.; Ottrey, A. L.; Onda, M.; Woodruff, M. Aust. J. Chem. 1983, 36, 639-648) as 100% standard, the central ring in 1 (averaged hond lengths 1.497, 1.343 Å) is 97.3% "bond fixed".
21. 1: Nambu, M.; Mohler, D. L.; Hardcastle, K.; Baldridge, K. K.; Siegel, J. S. J. Am. Chem. Soc. 1993, 115, 6138-6142.
22. Nucleus independent chemical shift (NICS) values for the central ring of 1: -1.1 ppm, the "cyclobutadiene" rings: -0.4 ppm, the terminal benzene nuclei: -10.7 ppm. Schulman, J. M.; Disch, R. L.; Jiao, H.; Schleyer, P. v. R. J. Phys. Chem. A 1998, 102, 8051-8055.
23. Most striking is the unusually high energy "stilbenoid" chromophore of 1 and the relatively highly shielded central carbons (δ 130.13 ppm; cf. biphenylene: δ 151.7 ppm, or the remaining four-membered ring carbons in 1: δ = 148.44 ppm).
24. (a) Mohler, D. L.; Vollhardt, K. P. C.; Wolff, S. Angew Chem., Int. Ed. Engl. 1995, 34, 563-565.
25. (b) Mohler, D. L.; Vollhardt, K. P. C.; Wolff S. Angew. Chem., Int. Ed. Engl. 1990, 29, 1151-1154.
26. For other, less structurally pronounced cyclohexatrienes, see: Komatsu, K. Eur. J. Org. Chem. 1999, 1495-1502 and references therein.
27. (a) Maksić, Z.B.; Eckert- Maksić, M.; Mó, O.; Yáñez, M. In Pauling's Legacy: Modern Modelling of the Chemical Bond; Maksić, Z. B., Orville-Thomas, W. J., Eds.; Elsevier: Amsterdam, 1999; pp 47-101 and references therein.
28. (b) Stanger, A. J. Am. Chem. Soc. 1998, 120, 12034-12040.
29. (c) Frank, N. L.; Siegel, J. S. In Advances in Theoretically Interesting Molecules; Thummel, R. P., Ed.; JAI: London, 1995; Vol. 3, pp 209-261.
30. (d) Faust, R.; Glendening, E. D.; Streitwieser, A.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1992, 114, 8263-8268.
31. See, inter alia: Shaik, S.; Shurki, A.; Danovich, D.; Hiberty, P. C. J. Mol. Struct. (THEOCHEM) 1997, 398-399, 155-167.
32. (a) Nambu, M.; Hardcastle, K.; Baldridge, K. K.; Siegel, J. S. J. Am. Chem. Soc. 1992, 114, 369-371.
33. (b) Nambu, M.; Siegel, J. S. J. Am. Chem. Soc. 1988, 110, 3675-3676.
34. (c) See also the data for 2 in refs 8 and 11. By the criterion described in ref 9, the central ring is 62% bond-localized.
35. (a) Diercks, R.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1986, 25, 266-268.
36. (a) Schulman, J. M.; Disch, R. L. J. Phys. Chem. A 1997, 101, 5596.
37. (b) Schulman, J. M.; Disch, R. L. J. Am. Chem. Soc. 1996, 118, 8470-8474.
38. (c) Maksić, Z. B.; Kovaček, D.; Eckert-Maksić, M.; Böckmann, M.; Klessinger, M. J. Phys. Chem. 1995, 99, 6410-6416.
39. (a) Benson, S. W. Thermochemical Kinetics, 2nd ed.; Wiley: New York, 1976.
40. (b) For updated numbers, see: Cohen, N. J. Phys. Chem. Ref. Data 1996, 25, 1411-1481.
41. For the details of the group increment calculations, see Supporting Information.
42. NIST Chemistry WebBook, NIST Standard Reference Database Number 69, November 1998, National Institute of Standards and Technology, Gaithersburg, MD 20899 (http://webbook.nist.gov).
43. George, P.; Trachtman, M.; Bock, C. W.; Brett, A. M. J. Chem. Soc., Perkin Trans. 1 1976, 1222-1227.
44. For enlightening exposés, see: (a) Liebman, J. F. In The Chemistry of Dienes and Polyenes; Rappoport, Z., Ed.; Wiley: New York, 1997; Vol. 1, pp 67-110. (b) George, P. Chem. Rev. 1975, 75, 85-111.
45. For enlightening exposés, see: (a) Liebman, J. F. In The Chemistry of Dienes and Polyenes; Rappoport, Z., Ed.; Wiley: New York, 1997; Vol. 1, pp 67-110. (b) George, P. Chem. Rev. 1975, 75, 85-111.
46. Roth, W. R.; Biermann, M.; Dekker: H.; Jochems, R.; Mosselman, C.; Hermann, H. Chem. Ber. 1978, 111, 3892-3903.
47. Deniz, A. A.; Peters, K. S.; Snyder, G. J. Science 1999, 286, 1119-1122, especially footnote 32.
48. We thank Professor Schulman for providing us with the geometric coordinates of calculated 7.
49. -1) is 174.0 kcal mol-1.
50. Benet-Buchholz, J.; Boese, R.; Haumann, T. In The Chemistry of Dienes and Polyenes; Rappoport, Z., Ed.; Wiley: New York, 1997; Vol. 1, pp 25-65.
51. See: Shepherd, M. K. Cyclobutarenes; Elsevier: Amsterdam, 1991.